Preparation of alkane sulfonyl chlorides from trialkylaluminum and sulfuryl chloride



United States Patent 3,373,192 PREPARATION OF ALKANE SULFONYL CHLO- RIDES FROM TRIALKYLALUMINUM AND SULFURYL CHLORIDE Pat W. K. Flanagan, Ponca City, Okla., assignor to Continental Oil Company, Ponca City, Okla, a corporation of Delaware N 0 Drawing. Filed Aug. 20, 1959, Ser. No. 834,958 7 Claims. (Cl. 260-543) This invention relates to the preparation of alkane sulfonyl chlorides and more particularly to the preparation of such compounds by the reaction of trialkylaluminum compounds with sulfuryl chloride.

Heretofore, methods for the preparation of sulfonyl chloride, using sulfuryl chloride as one of the reagents, have been confined to the reaction of that compound with a Grignard reagent. While alkane sulfonyl chlorides can be produced by these methods, these processes are not entirely satisfactory because Grignard reagents are rather expensive, are not readily available, and, furthermore, the yield of the desired product has been low. Generally, the yields at best have varied from 5 to 35%.

It is therefore a principal object of the present invention to provide a process that obviates the disadvantage of the prior art. It is another object of my invention to provide a process for the production of alkane sulfonyl chlorides from materials that are readily available in adequate quantities economically. It is another object of this invention to provide a convenient and easy operable process for the production of alkane sul'fonyl chlorides. It is another object of my invention to provide a process whereby primary alkane sulfonyl chlorides may be produced. It is another object of the present invention to provide a process whereby alkane sulfonyl chloride may be produced in a relatively pure condition. It is another object of my invention to provide a process whereby alkane sulfonyl chlorides can be produced in high yields. Other objects and advantages of the present invention will become apparent from the following description of my invention.

To the accomplishment of the foregoing and related ends, this invention then comprises the features hereinafter fully described and particularly pointed out in the claims, the following description setting forth in detail certain illustrative embodiments of the invention, these being indicative, however, of but a few of the various ways in which the principle of the invention may be employed.

Broadly stated, the foregoing objects and advantages are attained by a process which may be described briefly as follows: Sulfuryl chloride is reacted with a trialkylaluminum compound in the absence of air and in the presence of an inert organic solvent. After the completion of the reaction, the alkane sulfonyl chloride is recovered from the reaction mixture.

Before proceeding with specific examples illustrating my invention, it may be well to indicate in general the nature of the materials required in the process.

Suitable trialkylaluminum compounds include trimethyl, triethyl, tripropyl, etc., aluminum compounds. I prefer to employ trialkylaluminum compounds wherein the alkyl group contains from 6 to 18 carbon atoms, but compounds can be used wherein the alkyl group contains a larger number of carbon atoms. In addition to trialkylaluminum compounds, other aluminum organo compounds may be used, such as those identified by the general formulas AlR C1 and R AlOR wherein the Rs represent alkyl radicals containing from 1 to 18 or more carbon atoms. The alkyl groups of these compounds may be the same or diflerent.

Suitable solvents for dissolving the trialkylaluminum compound and the sulfuryl chloride include aromatic and aliphatic hydrocarbons and ethers. I prefer to employ a solvent that has a boiling point sutiiciently low so that it can be readily removed from the other components in the reaction mixture by distillation but high enough that losses through evaporation are not excessive. Also, if the solvent has low boiling point it will form explosive mix tures with air readily and as a consequence the use of such a compound can be hazardous. As a rule, suitable solvents are those having boiling points within the range of about 30 to 200 C. I prefer to use solvents having boiling points within the range of about 40 to C. Preferred solvents are the hydrocarbons, and it is not necessary to use a pure hydrocarbon, however, as mixtures are satisfactory.

As to the temperature of operation, that may vary from about 25 to C. For best results, I prefer to carry out the reaction over a more limited temperature range; namely, from 0 to 30 C.

Best results are obtained when approximately chemical equivalents of the reactants are used in the process as determined by the following equation:

As a general rule, I prefer to employ a slight excess of the sulfuryl chloride. It is very important to avoid having an excess of the alkyaluminum compound present in the reaction mixture.

As to the time of reaction, that is very rapid and varies inversely as temperature and varies from a few seconds to several hours. Specifically, when a reaction tempera ture of 100 is employed, the reaction is complete in a few seconds. On the other hand, if the reaction temperature is 25" C., several hours time will be required for the reaction to go to completion. When the process is operated within the preferred temperature range (0 to 30 C.), the time of reaction varies from 15 minutes to 2 hours.

The reaction is carried out in the absence of air, and this is accomplished by maintaining the entire reaction under an atmosphere of an inert gas. Suitable gases for this purpose include any gas that will not react with any of the reactants present. This will include the noble gases and nitrogen.

In order to disclose the nature of the present invention still more clearly, the following illustrative examples will be given. It is to be understood that the invention is not to be limited to the specific conditions or details set forth in these examples except insofar as such limitations are specified in the appended claims.

In the examples, parts by weight bear the same relation to parts by volume as do grams to cubic centimeters.

Example 1 A solution of 161 parts by weight of sulfuryl chloride dissolved in 200 parts by volume of hexane was placed in a reaction vessel. After the air in the reaction vessel was replaced with nitrogen, 260 parts by weight of trioctylaluminum was added thereto slowly with stirring while the temperature was maintained between 15 to -25 C. After the addition was completed, the reaction mixture was allowed to stand /2 hour at room temperature and then the aqueous layer extracted with 100 parts by volume of hexane. The hexane was removed under a vacuum and the l-octanesulfonyl chloride recovered in a yield of 75% of theory. Analysis of the recovered product showed that the chlorine content was 16.06% as contrasted to theoretical chlorine content of 16.71%. It exhibited characteristic infrared absorption bands at 7.25 and 8.56 microns.

Example 2 A solution of 96 parts by weight of sulfuryl chloride dissolved in parts of hexane was placed in a reaction vessel. After the air was replaced with nitrogen 240 parts 3 by weight of trioctadecylaluminum was added to the contents in the reaction vessel. The procedure was similar to the procedure used in Example 1 with the exception that the temperature was maintained within a range of to 25 C. In the end of the reaction, the reaction mixture was poured onto 400 parts by weight of ice producing a white precipitate. The mixture was heated on a steam bath and hexane was added until the precipitate dissolved. The hexane layer was separated and, after cooling and evaporating the hexane, l-octadecanesulfonyl chloride was obtained in a good yield. Analysis of this product showed that it contained 9.95% chlorine as against 10.07% on a calculated basis. The product exhibited characteristic infrared absorption bands at 7.35 and 8.65 microns.

Additional examples were run in which tributylaluminum, tripropylalurninurn, and tridodecylaluminum were the specific trialkylaluminum compounds used. In each example, good yields of the alkane sulfonyl chloride were obtained.

While particular embodiments of the invention have been described, it will be understood, of course, that the invention is not limited thereto since many modifications may be made, and it is, therefore, contemplated to cover by the appended claims any such modifications as fall within the true spirit and scope of the invention.

The invention having thus been described, what is claimed and desired to be secured by Letters Patent is:

1. A process for the preparation of an alkane sulfonyl chloride which comprises reacting a trialkylaluminum compound with sulfuryl chloride wherein the alkyls in said alkyl aluminum compound contains from 1-18 carbon atoms therein, and wherein said trialkylaluminum compound is added under an atmosphere of an inert gas to sulfuryl chloride at a temperature within the range of 25 to 100 C. in the presence of an inert organic solvent, cooling the resultant reaction mixture, and then recovering the alkane sulfonyl chloride.

2. The process according to claim 1 wherein the inert organic solvent boils in the range varying from about 30 to about 200 C.

3. The process of claim 1 wherein the alkylaluminum compound is trioctadecylaluminum.

4. The process of claim 1 wherein the alkylaluminum compound; is triethylaluminum.

5. The process of claim 1 wherein the alkylaluminum compound is tributylaluminum.

6. The process of claim 1 wherein the alkylaluminum compound is tripopylaluminum.

7. The process of claim 1 wherein the alkylaluminum compound is tridodecylaluminum.

References Cited UNITED STATES PATENTS Chemistry Series, No. 23, p. 166 A.C.S. (1959).

Tohl et al.: Ber. Deut..Chem., volume 26, pp. 2940- 2945 (1893).

Rochow et al.: The Chemistry of the Organometallic Compounds, 1957, pp. 279280.

LORRAINE A. WEINBERGER, Primary Examiner.

LEON ZITVER, C. B. PARKER, Examiners.

HAROLDC. WEGNER, B. M. EISEN, F. D. HIGEL,

I. W. WILLIAMS, Assistant Examiners. 

1. A PROCESS FOR THE PREPARATION OF AN ALKANE SULFONYL CHLORIDE WHICH COMPRISES REACTING A TRIALKYLALUMINUM COMPOUND WITH SULFURYL CHLORIDE WHEREIN THE ALKYLS IN SAID ALKYL ALUMINUM COMPOUND CONTAINS FROM 1-18 CARBON ATOMS THEREIN, AND WHEREIN SAID TRIALKYLALUMINUM COMPOUND IS ADDED UNDER AN ATMOSPHERE OF AN INERT GAS TO SULFURYL CHLORIDE AT A TEMPERATURE WITHIN THE RANGE OF -25 TO 100%C. IN THE PRESENCE OF AN INERT ORGANIC SOLVENT, COOLING THE RESULTANT REACTION MIXTURE, AND THEN RECOVERING THE ALKANE SULFONYL CHLORIDE. 